Liquefaction co-processing of coal shale oil at - Argonne National ...

catalytic to the thermal hydrogenation shows increases in the hydrogen content in
both PS and BS fractions with NiMo/Alz03. Thus, it appears that the increased
hydrogen consumption resulted in a direct increase of the hydrogen content of the
products. Comparison of the gas chromatograms obtained from both the PS and 8s
fractions prior to the reaction to that obtained after the thermal and catalytic
reactions, however, did not show any visible changes in the product fingerprint.
Changes in the compounds present or the addition of new compounds to these product
fractions was not discernible in the chromatograms.
Table 2
Elemental Composition of PS and 8s Fractions from Upgrading Fractions
Temperature PS BS
Reactants OC Catalyst % C % H % C XH
Maya TLR No Reaction 84.7
84.7
11.5
11.4
NM*
NM
NM
NM
Maya TLR 400 None 85.7
85.6
11.2
11.4
82.8
83.1
7.0
7.0
Mava TLR 400 NiMo/A1902 ' &.I 87.1
86.8
12.0
11.8 83.9 8.5
Maya TLR 400 Mo Naphthenate 84.9 11.3 82.7 6.5
84.6 11.2 82.9 7.6
-~ -.
Maya TLR
Maya TLR
+ . TFT
425
No Reaction
Mo Naphthenate 86.1
88.0
86.9
11.8
12.1
10.0
85.3
85.3
NM
7.4
7.3
NM
Maya TLR
+ TET
Maya TLR
+ TET
Maya TLR
+ TET
400
400
425
None
NiMo/A1203
Mo Naphthenate
86.6
86.7
87.9
87.6
86.8
87.0
10.2
10.3
10.9
10.8
10.3
10.3
83.6
83.6
79.3
78.2
84.9
84.3
7.3
6.8
8.7
8.4
7.3
7.4
*NM: Not measured
When TET was added, a higher oil production (53.5%) and a decrease in BS were
observed, although the total amount of heavy products (MCMS, THFS, and IOM) was
similar to the reaction without TET. In these reactions, the catalyst and TET
were both positive factors in producing PS materials. The molecular hydrogen
consumed by the residuum was nearly equivalent to the reaction without TET. Only
0.39 mmoles of NAPH were produced which was approximately one-sixth that produced
in the thermal reaction, indicating that hydrogenation of NAPH formed during the
reaction to TET occurred in the presence of NiMo/AlzO3.
The catalytic upgrading reactions with Mo naphthenate were performed at 400
and 425OC. Compared to the thermal reaction, only a small change in product
slate was observed with Mo naphthenate at 400 OC. At an increased reaction
temperature of 425OC, the activity of the Mo naphthenate catalyst appeared to be
enhanced since substantial increases in the upgrading of Maya TLR were observed;
BS was converted to PS and only small amounts,